Sulfonyl ethylene fungicides



United States Patent Office 3,044,926 SULFONYL ETHYLENE FUNGICDES JamesP. Flavin, Mission, and Joseph R. Riden, Jr., Overland Park, Kans.,assignors to Chemagro Corporation, New York, N.Y., a corporation of NewYork No Drawing. Filed May 29, 1958, Ser. No. 738,659 Claims priority,application France May 21, 1958 19 Claims. (Cl. 167-22) The presentinvention relates to new ethenyl sulfones and to their use primarily asfungicides, but also as pesticides to control other pests, e.g., asbactericides, nematocides and even as insecticides and weedicides.

It is an object of the present invention to prepare novel ethenylsulfones.

Another object is to provide compositions containing ethenyl sulfoneswhich have outstanding utility in protecting a wide variety of materialsfrom fungi.

An additional object is to provide compounds which afford protectionagainst a wide range of pests.

A further object is to provide compositions containing ethenyl sulfoneswhich have outstanding utility in protecting a wide variety of materialsfrom bacteria.

Still another object is to provide ethenyl sulfone compositions whichprotect plants .against nematodes.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by thepreparation of ethenyl sulfones of the formula where R R and R are eachalkyl groups and X is a halogen of atomic Weight not over 80, Le.fluorine, chlorine or bromine, or hydrogen. The preferred compounds arethose where X is chlorine or hydrogen. Preferably R R and R are loweralkyl groups, generally of 1 to 8 carbon atoms and most desirably notover 4 carbon atoms.

Typical examples of compounds which can be made and used according tothe present invention are tris- (methylsulfonyl) ethylene;tris(methylsulfonyl) chloroethylene; tris(methylsulfonyl) bromoethylene;tris(methylsulfonyl) fiuoroethylene; tris(ethylsulfonyl) ethylene;tris(ethylsulfonyl) chloroethylene; tris(n-propylsulfonyl) ethylene;tris(n-propylsulfonyl) ethylene; tris(n-propylsulfonyl) chloroethylene;tris(isopropylsulfonyl) ethylene; tris(isopropylsulfonyl)chloroethylene; tris(n-butylsulfonyl) ethylene; tris(n-butylsulfonyl)chloroethylene; tris(isobutylsulfonyl) ethylene; tris(isobutylsulfonyl)chloroethylene; tris(sec. butylsulfonyl) ethylene; tris- (sec.butylsulfonyl) chloroethylene; tris(tert. butylsulfonyl) ethylene;tris(tert. butylsulfonyl) chloroethylene; tris(n-amylsulfonyl) ethylene;tris(n-amylsulfonyl) chloroethylene; tris(n-hexylsulfonyl) ethylene;tris(n-hexylsulfonyl) chloroethylene; tris(n-octylsulfonyl) ethylene;tris(n-cctylsulfonyl) chloroethylene; tris(Z-ethylhexylsulfonyl)ethylene; tris(Z-ethylhexylsulfonyl) chloroethylene; tris(ndecylsulfonyl) ethylene; tris(n-decylsulfonyl) chloroethylene;tris(dodecylsulfonyl) ethylene; tris(noctadecylsulfonyl) ethylene;tris(n-octadecylsulfonyl) chloroethylene; l,2-di(methyl sulfonyl)l-n-propylsulfonyl ethylene; and l-methyl sulfonyl-Z-ethyl sulfonyl-2-propylsulfonyl chloroethylene.

The compounds of the invention are effective as pesticides forcontrolling fungi, bacteria, smuts, mildew, nematodes and otherorganisms in the class of plant pests.

The compounds of the present invention are also uses ful forprotectingcloth, leather, Wood and painted surfacesfrom attack by fungiand other organisms. While it is possible to apply the compounds of thepresent invention in undiluted form to the plant or other material to beprotected, it is frequently desirable to apply the novel sulfones inadmixture with either solid or liquid inert, pesticidal adjuvants. Thus,the sulfones can be applied to the plants for fungicidal purposes, forexample,

by spraying them with aqueous or organic solvent dispersions of thesulfone. Similarly, wood surfaces canbe protected by applying aprotective film of the sulfone by brushing, spraying or dipping,utilizing a liquid dispersion of the sulfone. The choice of anappropriate solvent is determined largely by the concentration of activeingredient which it is desired to employ, by the volatility required ina solvent, the cost of the solvent and the nature of the material beingtreated. Among the many suitable organic solvents which can be employedas carriers for the present pesticides, there may be mentionedhydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil,fuel oil, petroleum, naphtha, ketones such as acetone, methyl ethylketone and cyclohexanone, chlorinated hydrocarbons, such as carbontetrachloride, chloroform, trichloroethylene, perchloroethylene, esterssuch as ethyl acetate, amyl acetate and .butyl acetate,.,the monoalkylethers of ethylene glycol, e.g., the monomethyl ethers and the monoalkylethers of diethylene glycol, e.g., the monoethyl ether, alcohols such asethanol, isopropanol and amyl alcohol, etc.

The sulfones can also be applied to plants and other materials alongwith inert solid fungicidal adjuvants or carriers such astalc,pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth,lime, calcium carbonate, bentonite, fullers earth, cottonseed hulls,wheat flour, soybean flour, etc., pumice, tripoli, wood flour, Walnutshell flour and lignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of this invention. Such surface active agentsare advantageously employed in both the solid and liquid compositions.The surface active agent can be anionic, cationic or nonionic incharacter.

Typical classes of surface active agents include alkyl sulfonates,alkylaryl sulfonates, alkyl sulfates, alkylamide sulfonates, alkylarylpolyether alcohols, fatty acid esters of polyhydric alcohols, ethyleneoxide addition products of such esters; addition products of long chainmercaptans and ethylene oxide; sodium alkyl benzene sulfonates having 14to 18 carbon atoms, alkylphenolethylene oxides, e.g., p-isooctyl phenolcondensed with 10 ethylene oxide units; and soaps, e.g., sodium stearateand sodium oleate. Typical surface active agents are: Aerosol OS (sodiumsalt of propylated naphthalenesulfonic acid); AerosolOT[(di-Z-ethylhexyl) ester of sodium sulfosuccinic acid]; Alkanol B(sodium alkylnaphthalene sulfonate); Alrosene 31 (sodium salt ofmodified alcohol sulfate from cocoanut fatty acids); Arctic Syntex'M(sodium salt sulfonated monoglyceride of cocoanut fatty acids); Areskap[oHOC H C H (C H (SO;;=Na)]; Areskap 300 4 9) 's e s e sl ethyleneglycol lauryl ether); Daxad No. 11 (sodium salt of polymerized alkylatedarene sulfonic acid); Duponol Patented July 17, 1962 LS (sodium oleylsulfate); Duponol WA (sodium lauryl sulfate); Emulsept N-OH2 011 23N-CHz CHzCHzONa CHzC O 0N8 Myrj (polyethylene glycol stearate); NacconolNR (sodium dodecyl benzene sulfonate); Wekal A (sodium salt ofisopropylated naphthalenesulfonic acid); Nekal BX (sodium salt ofbutylated naphthalenesulfonic acid); Ninol 1281 (fatty acidethanolamide); Nonic 218 (tertiary dodecyl polyethylene glycolthioether); Pluronics (condensation product of ethylene oxide andpolypropylene glycol); Renex 25 (solidifiedurea complex of polyethyleneglycol ester of mixed fatty and resin acids); Santomerse No. 1 (sodiumdodecyl benzenesulfonate); Santomerse D (sodium decyl benzenesulfonate);Santomerse B Sapamine KW [CH CH 7CH:CH (CH C0 NHCH CH N 3) a s) 2] l ss] Span 20 (sorbitan monolaurate); Span 40 (sorbitan monopalmitate);Span 60 (sorbitan monostearate); Span 80 (sorbitan monooleate); SteroxCD (polyethylene glycol ester of tall oil acids); Snlframin DR (sodiumsalt of sulfonated condensation product of ethanolamine with a fattyacid); Tergitol 08 [C H CH(C H )CH OSO Na]; Tergitol4 [C H CH(C H CH CHCH (CH CH (CH OSO Na] Tergitol 7 Triton [p-C H 7C H4(OCH2CH2)2OSO3N3.where C H is diisobutyl]; Triton X-lOO Tween 20 [tris(polyoxyethylene)sorbitan monolaurate]; Tween 40 [tris(giolyoxyethylene) sorbitanmonopalmitate]; Tween 60 [tris(polyoxyethylene) sorbitan monostearate];Tween 80 [tris(polyethylene) sorbitan monooleate]; Ultrawet SK (sodiumalkylbenzene sulfonate) Ultravon K (sodium salt of sulfonated alkylbe'nzimidazole); Aerosol MA (sodium dihexyl sulfosuccinate); Nekal BV(sodium dibutyl naphthalenesulfonate); Dreft (an alkyl sulfate); andTurkey red oil.

The solid and liquid formulations can be prepared in any suitablemethod. Thus, the active ingredients, in finely divided form if a solid,may be tumbled together with finely divided solid carrier.Alternatively, the active ingredient in liquid form, includingsolutions, dispersions, emulsions and suspensions thereof, may beadmixed with the solid carrier in finely divided form in amounts smallenough to preserve the free-flowing prop erty of the final dustcomposition.

When solid compositions are employed, in order to obtain a high degreeof coverage with a minimum dosage of the formulation, it is desirablethat the formulation be in finely divided form. The dust containingactive ingredient usually should be sutficiently fine that substantiallyall will pass through a 20 mesh Tyler sieve. A dust which passes througha 200 mesh Tyler sieve also is satisfactory.

For dusting purposes, preferably formulations are employed in which theactive ingredient is present in an amount of S to 50% of the total byweight. However,. concentrations outside this range are operative andcompositions containing from 1 to 99% of active ingredient by weight arecontemplated, the remainder being carrier and/or any other additive oradjuvant material which may be desired. It is often advantageous to addsmall percentages of surface active agents, e.g., 0.5 to 1% of the totalcomposition by weight, to dust formulations, such as the surface activeagents previously set forth.

For spray application, the active ingredient may be dissolved ordispersed in a liquid carrier, such as water or other suitable liquid.The active ingredient can be in the form of a solution, suspension,dispersion or emulsion in aqueous or non-aqueous medium. Desirably, 0.5to 1.0% of a surface active agent by weight is included in the liquidcomposition.

For adjuvant purposes, any desired quantity of surface active agent maybe employed, such as up to 250% of the active ingredient by weight. Ifthe surface active agent is used only to impart wetting qualities, forexample, to the spray solution, as little as 0.05% by weight or less ofthe spray solution need be employed. The use of larger amounts ofsurface active agent is not based upon wetting properties but is afunction of the physiological behavior of the surface active agent.These considerations are particularly applicable in the case of thetreatment of plants. In liquid formulations the active ingredient oftenconstitutes not over 30% by weight of the total and may be 10%, or evenas low as 0.01%.

The novel sulfones of the present invention can be employed incompositions containing other pesticides, more especially fungicides,insecticides and bactericides, e.g., phenothiazine, pyrethrum, rotenone,DDT, etc.

The novel sulfones of the present invention can be prepared by reactinga mercaptan having the formula RSH where R is an alkyl group with asubstituted ethylene having the formula where at least threesubstituents are halogen of atomic weight not over 80 and the remainingsubstituent is such a halogen or hydrogen to form an ethenyl typesulfide followed by oxidation of this sulfide to the correspondingsulfone. The oxidation of the sulfide is preferably carried out withhydrogen peroxide. However, other oxidizing agents can be used such aspermanganates, e.g., potassium permanganate, chromic acid, nitric acid,bypochlorites, e.g., sodium hypochlorite, organic peroxides,

e.g., benzoyl peroxide, etc. The oxidation frequently is bonates,bicarbonates and organic bases.

carried out in an organic solvent.

The preliminary reaction of the mercaptan with the polyhalo substitutedethylene is carried out in the presence of an acid acceptor such asalkali hydroxides, car- Typical acid acceptors include sodium hydroxide,potassium hydroxide, barium hydroxide, sodium carbonate, potassiumcarbonate, sodium bicarbonate, tetraethyl ammonium hydroxide, etc.Preferably, an organic solvent is also present, e.g., ethyl alcohol,methyl alcohol, n-butanol, etc.

The general scheme of the reaction is illustrated below.

In the specification and claims unless otherwise indicated all parts andpercentages are by weight.

Unless otherwise indicated the hydrogen peroxide concentration in theexamples is 30%.

EXAMPLE 1 Bis(n-Propylsulfonyl)-1-Chl0r0ethylene andTris(n-Propylsulfonyl) Ethylene Trichloroethylene 260 g. (2 mol)n-Propylmercaptan 76 g. 1 mol) Sodium hydroxide :60 g. (1.5 mol) Thetrichloroethylene was mixed with 100 ml. of alcohol andthen a mixture ofthe n-propyl mercaptan and sodium hydroxide dissolved in 300 ml. ofalcohol were added dropwise. The mixture was heated to 70 C. and afteraddition of all the material was refluxed for an hour. The sodiumchloride was filtered olf and the alcohol removed under aspiratorvacuum. Two volumes of Water were added and the mixture thenextractedwith 3 volumes of benzene. The benzene was distilled off under aspiratorvacuum.

The product was then distilled under aspirator vacuum to give 3fractions. The first fraction distilled at 77- 120 C.; the secondfraction distilled at l20-l44 C. and the third fraction was the highboiling residue.

There were then separately oxidized 20 g. of the first fraction, g. ofthe second fraction and g. of the third fraction, using in each case 30ml. of glacial acetic acid and 30 ml. of 35% hydrogen peroxide at 70 C.for 2 hours.

The oxidized first fraction was primarily n-propylsulfonyl1,2-dichloroethylene. The oxidized second fraction was primarilybis(n-propylsulfonyl) chloroethylene.

The oxidized third fraction was primarily tris(n-propy1- sulfonyl)ethylene. It was observed that the impure mixtures obtained as thefractions in this example could he successfully used as fungicides inthe same manner as the pure compounds.

'6 EXAMPLE 2 Tris(n-Propylsulfonyl) Ethylene Trichloroethylene 1.30 g.(1 mol) n-Propyl mercaptan 228 g. (3 mol) Sodium hydroxide 120 g. (3mol) The procedure of Example 1 was repeated to obtain substantiallypure tris(n-pr0pylsulfonyl) ethylene.

EXAMPLE 3 Tris(n-Propylsulfonyl) Chloroethylene The trichloroethylene ofExample 2 was replaced by 166 g. of tetrachloroethylene and the productobtained was tris(n-propylsulfonyl) chloroethylene.

EXAMPLE 4 Bis(Ethylsulfonyl) Chloroethylene and Tris(Eth-ylsulfonyl)Ethylene Trichloroethylene 260 g. (2 mol). Ethyl mercaptan .62 g. (1mol) Sodium hydroxide 50 g. (1.25 mol) The trichloroethylene was mixedwith 200 ml. of ethyl alcohol and there were added the sodium hydroxidein 200 ml. of ethyl alcohol followed by the mercaptan. Ethyl alcohol wasadded until all the materials were in solution. The addition of themercaptan and sodium hydroxide was accomplished at reflux over a periodof 1 hour. The mixture was further refluxed for 3 hours, cooled, thesodium chloride filtered off, 500 m1. of alcohol removed by distillationand the mixture taken up in 2 volumes of water and extracted with 4volumes of benzene. The benzene was distilled off and the mixturefractionally distilled under aspirator vacuum to give the followingproducts:

B.P., C. Ethyltbio 1,2-chloroethylene 78-83 Bis(ethylthio-dichloroethylene 92 Tris(ethylthio) ethylene 132 Ten grams of thebis(ethylthio) chloroethylene was oxidized with 0.5 mol of hydrogenperoxide in glacial acetic acid at C. to obtain bis(ethylsulfonyl)chloroethylene. f

In similar fashion 18 g. of the tris(ethylthio) ethylene was oxidizedwith 0.4 mol of hydrogen peroxide in of trichloroethylene to 200 ml. ofethyl alcohol and slowly adding 76 g. (1 mol) of isopropyl mercaptan and50 g. (1.25 mols) of sodium hydroxide dissolved in 400 ml. of ethylalcohol. The mercaptan'was added over 1 hour and the mixture wasrefluxed for 3 more hours. The sodium chloride was filtered off, thealcohol taken off and then water was added and the mixture extractedwith benzene and washed with water. The benzene was removed atatmospheric pressure'and several cuts were distilled over at aspiratorpressure. The cuts boiling below 129 C. were discarded and the cutboiling at l29'139 C.- recovered. This cut'was a mixture containingtris(isopropylthio) ethylene together wtih some bis(isopropylthio)chloroethylene. 12.5 g. of the cut was oxidized with 45 ml. of 35%hydrogen peroxide and 30ml; of acetic acid at 90 C. for 2 hours toobtain tris(isopropyl sulfonyl) ethylene asan oil.

EXAMPLE 6 Tris(Methylsulfonyl) Ethylene Example 5 was repeated usingdouble The isopropyl mercaptan was replaced by 100 g. of methylmercaptan. The tris(methylthio) ethylene had a BI. range of 1l5-l40 C.at the aspirator and contained some bis(methylthio) chloroethylene.

To 166 gms. of the tris(methylthio) ethylene were added 90 ml. of 35%hydrogen peroxide and 30 ml. of acetic acid. The mixture was held at90-95" C. with stirring for 2 hours and the tris(methylsulfonyl)ethylene recovered as an oil.

Typical examples of suitable formulations are given below.

EXAMPLE 7 A wettable powder fungicide was made from 20%tris(n-propylsulfonyl) ethylene, 38% diatomaceous earth, 40% kaolin clayand 2% sodium N-methyl-N- oleoyl taurine (wetting agent). The mixturewas ground so that over 90% passed through a 325 mesh U.S. standardsieve.

In place of the tris(n-propylsulfonyl) ethylene formulation of thisexample there were also made up three other formulations which wereidentical except that the tris- (n-propylsulfonyl) ethylene Was replacedby an equal weight of tris(n-propylsulfonyl) chloroethylene in the firstcase, by an equal weight of tris(n-butylsulfonyl) ethylene in the secondcase and t1is(methylsulfonyl) ethylene in the third case.

EXAMPLE 8 A granular fungicide comprising of tris(isopropylsulfonyl)ethylene as the active compound and 95% of calcined diatomaceons earthof 20 to 70 mesh size (U.S. standard sieve) as a granular absorbentdiluent was prepared by spraying the sulfone in liquid state on thegranules with mixing.

In place of the tris(isopropylsulfonyl) ethylene formulation of thisexample there were also made up two other formulations which wereidentical except that in one case the tris(isopropylsulfonyl) ethylenewas replaced by an equal amount of tris (methylsulfonyl) ethylene and inthe other case tris(ethylsulfonyl) ethylene was used as the replacement.

EXAMPLE 9 An emulsifiable spray concentrate fungicidepreparationcomprising 48 grams of tris(methylsulfonyl) ethylene, 10 grams ofpolyoxyethylene sorbitan monolaurate (Tween 20), as an emulsifier andsufiicient xylene to make the mixture up to 100 ml. was prepared bystirring the ingredients together. Ln place of the tris(methylsulfony-l)ethylene concentrate of this example there were also made up two otherconcentrates which were identical except that in one case thetris(:rnethylsulfonyl) ethylene was replaced by an equal amount oftn's(ethylsulfonyl) ethylene while in the other casetris(isopropylsulfonyl) ethylene was used as a replacement.

EXAMPLE 10 The three spray concentrates of Example 9 were each dilutedwith 480 liters of water to give an aqueous emulsion containing 100 ppm.of active ingredient in each case.

Satisfactory results have also been obtained for example, by emulsifyingthe sulfones directly in water without the addition of an organicsolvent. Thus one part of tris(n-butylsulfonyl) ethylene can beemulsified in 100 parts of water directly with the aid of 0.1 part ofpolyoxyethylene sorbitol (Atlox 1045).

The compounds of the present invention were tested as soil fungicides asshown in Table I. The chemical to be tested was mixed with soilnaturally infested with Pythium spp. Pea seeds were planted and theefficiency of the chemicals noted as percent emergence.

TABLE I Lbs. of chemical/acre Chemical 200 100 50 25 12.5 6. 25

tris(methylsulfonyl) ethylene... 100 100 100 40 tris(ethylsulfonyl)ethylene. 100 100 60 tris(isopropylsultonyl) ethylene. 90 90 20 0 Thecompounds of the present invention also are good seed disinfectants,being in a class with the mercurials in this respect. Table II shows theresults as a seed disinfectant using oat seeds naturally infested withHelminthosporium victoriae. The results are expressed as percent controlof this fungus which causes Victoria blight.

TABLE II Ounces/bushel Chemicals tris(methylsull0nyl) ethylene, percent"20 tris(ethylsulionyl) ethylene, pcrcent. 100 90 tris(isopropylsulfonyl)ethylene, per- 40 0 cent wherein R R and R are each alkyl groups and Xis selected from the group consisting of a halogen of atomic weight notover 80 and hydrogen.

2. A compound according to claim 1 wherein R R and R are each alkylgroups having 1 to 18 carbon atoms. 3. A compound according to claim 1wherein X is hydrogen.

4. A compound according to claim 1 wherein R R and R each have 1 to 4carbon atoms and X is hydrogen. 5. A compound according to claim 1wherein R R and R each have 1 to 8 carbon atoms.

6. A compound according to claim 5 wherein X is hydrogen.

7. A compound having the formula C: SO2Rz wherein R R and R are eachalkyl groups and X is a halogen selected from the group consisting offluorine, chlorine and bromine.

8. A pesticidal composition comprising a compound having the formulaC=CSOaRa wherein R R and R are each alkyl groups and X is selected fromthe group consisting of a halogen of atomic weight not over 80 andhydrogen together with a surface active agent.

9. A composition according to claim 8 wherein X is hydrogen.

10. A composition according to claim 8 wherein R R and R each have 1 to4 carbon atoms and X is hydrogen.

11. A composition according to claim 8 wherein R R and R each have 1 to8 carbon atoms.

12. A composition according to claim 11 wherein X is hydrogen.

13. A process for killing fungi comprising applying to the fungi habitatan effective amount of a compound having the formula C=C-SOaRa R SOgwherein R R and R are each alkyl groups and X is selected from the groupconsisting of a halogen of atomic weight not over 80 and hydrogen.

-14. A process according to claim 13 wherein X is hydrogen.

15. A process according to claim 14 wherein R R and R each have 1 to 8carbon atoms.

16. A process according to claim 14 wherein R R and R each have 1 to 4carbon atoms.

17. A process for protecting material from attack by fungi comprisingapplying to said material an effective amount of tris(alkylsulfonyl)ethylene.

wherein R R R are each alkyl groups and X is a halo gen selected fromthe group consisting of fluorine, chlorine and bromine.

References Cited in the file of this patent UNITED STATES PATENTSSchoene Jan. 3, 1950 Raasch July 7, 1959 OTHER REFERENCES Schneider:Chemische Berichte, 84, 911-916 (esp. p. 916), 1951.

Frear: A Catalogue of Insecticides and Fungicides, vol. I, page 58,1947, Chronica Botanica Co.

13. A PROCESS FOR KILLING FUNGI COMPRISING APPLYING TO THE FUNGI HABITATAN EFFECTIVE AMOUNT OF A COMPOUND HAVING THE FORMULA